EP0544531A1 - Verfahren zur Herstellung von Epsilon-Caprolactam durch Beckmann-Umlagerung in der Gasphase in der Gegenwart eines Zeolithkatalysators und einer stickstoffhaltigen Verbindung - Google Patents
Verfahren zur Herstellung von Epsilon-Caprolactam durch Beckmann-Umlagerung in der Gasphase in der Gegenwart eines Zeolithkatalysators und einer stickstoffhaltigen Verbindung Download PDFInfo
- Publication number
- EP0544531A1 EP0544531A1 EP92310819A EP92310819A EP0544531A1 EP 0544531 A1 EP0544531 A1 EP 0544531A1 EP 92310819 A EP92310819 A EP 92310819A EP 92310819 A EP92310819 A EP 92310819A EP 0544531 A1 EP0544531 A1 EP 0544531A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- reaction
- nitrogen
- caprolactam
- ether
- cyclohexanone oxime
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 239000010457 zeolite Substances 0.000 title claims abstract description 9
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title claims description 26
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000007789 gas Substances 0.000 claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 9
- 150000003956 methylamines Chemical class 0.000 claims abstract description 8
- 239000011949 solid catalyst Substances 0.000 claims abstract description 7
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 91
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 150000001298 alcohols Chemical class 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002026 crystalline silica Inorganic materials 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- RMGHERXMTMUMMV-UHFFFAOYSA-N 2-methoxypropane Chemical compound COC(C)C RMGHERXMTMUMMV-UHFFFAOYSA-N 0.000 claims description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 2
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- VNKYTQGIUYNRMY-UHFFFAOYSA-N methoxypropane Chemical compound CCCOC VNKYTQGIUYNRMY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 31
- 229910001873 dinitrogen Inorganic materials 0.000 description 15
- 239000003575 carbonaceous material Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 150000002170 ethers Chemical class 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003570 air Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000006462 rearrangement reaction Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000006237 Beckmann rearrangement reaction Methods 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/02—Preparation of lactams
- C07D201/04—Preparation of lactams from or via oximes by Beckmann rearrangement
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to a process for producing ⁇ -caprolactam from cyclohexanone oxime using solid catalysts under gas phase reaction conditions.
- ⁇ -Caprolactam is an important raw material for nylon and the like.
- the inventors have proposed processes for producing ⁇ - caprolactam by rearrangement of cyclohexanone oxime (Beckmann rearrangement) using solid catalysts under gas phase reaction conditions in the presence of lower alcohols and/or ether compounds (Japanese Patent Kokai Nos. Hei 2-275850 and 2-250866).
- the inventors have further conducted intensive research on a rearrangement reaction of cyclohexanone oxime and have found that when the rearrangement reaction is carried out in the presence of specific nitrogen-containing compounds in the reaction system, ⁇ -caprolactam is obtained with a high selectivity and life of the catalysts are greatly prolonged even under such conditions that cyclohexanone oxime reacts with high conversion. As a result, the present invention has been accomplished.
- the present invention provides an industrially superior process for producing ⁇ -caprolactam which comprises bringing cyclohexanone oxime into contact in a gas phase with solid catalysts in the presence of at least one nitrogen-containing compound selected from ammonia, methylamines and ⁇ -caprolactam.
- the solid catalysts used in the present invention include, for example, silica-alumina and zeolites and in particular, crystalline silica and crystalline metallosilicates are preferred.
- the crystalline silica used in the present invention comprises substantially silicon and oxygen.
- the crystalline metallosilicates contain metals in addition to silicon and oxygen, such as those which have a ratio of the number of silicon atom to that of metal atoms (Si/metal atomic ratio) of 5 or higher, preferably at least 500.
- the metals mention may be made of at least one metal selected from Al, Ga, Fe, B, Zn, Cr, Be, Co, La, Ge, Ti, Zr, Hf, V, Ni, Sb, Bi, Cu and Nb.
- the Si/metal atomic ratio is obtained by usual analytical methods such as atomic absorption spectrometry and X-ray fluorescence analysis. These catalysts are prepared by known processes.
- the crystalline silica and crystalline metallosilicates have various crystalline forms and those which belong to pentasil type structure are preferred.
- the process of the present invention is characterized in that a specific nitrogen-containing compound is allowed to exist in the reaction system.
- the nitrogen-containing compounds include at least one compound selected from ammonia, methylamines and ⁇ -caprolactam. Among them, ammonia and methylamines give preferable results.
- the methylamines include, for example, monomethylamine, dimethylamine and trimethylamine.
- Amount of the nitrogen-containing compounds is usually 10 moles or less, preferably 1 mole or less, more preferably 0.001-0.8 mole per mol of cyclohexanone oxime used.
- alcohols or ether compounds may be allowed to exist in the reaction system, in order to improve selectivity of the desired product.
- the alcohols and ether compounds include the compounds represented by the following formula (1).
- R1-O-R2 (1) (wherein R1 represents a C1-C6 alkyl group (hereafter a lower alkyl group) which may be substituted with at least one fluorine atom and R2 represents a hydrogen atom or a C1-C6 alkyl group (hereafter a lower alkyl group) or a phenyl group which may be substituted with at least one fluorine atom).
- the lower alcohols are methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, n-amyl alcohol, n-hexanol and 2,2,2-trifluoroethanol. Methanol and ethanol are preferred.
- the ether compounds are preferably those which have a methyl group or an ethyl group as R1 in the formula (1).
- Examples of preferred ether compounds of 8 or less carbon atoms are dimethyl ether, methylethyl ether, diethyl ether, methyl-n-propyl ether, methylisopropyl ether, methyl-tert-butyl ether and anisole. Two or more of alcohols or two or more of ether compounds may be used. Alcohols may also be mixed with ether compounds.
- vapors of compounds inert to the reaction such as benzene, cyclohexane and toluene or inert gases such as nitrogen and carbon dioxide may also be allowed to coexist as a diluent gas.
- the starting material cyclohexanone oxime is subjected to the catalytic reaction in the gas form.
- the reaction is carried out in either a fixed-bed or fluidized bed.
- the nitrogen-containing compounds may be mixed or not with cyclohexanone oxime before they are fed to a reactor. When the nitrogen-containing compounds are not mixed with cyclohexanone oxime before feeding, the nitrogen-containing compounds may be fed in portions. In the case of the fixed-bed reaction, it is preferred to pass a thorough mixture of the cyclohexanone oxime and the nitrogen-containing compounds through the catalyst bed.
- Reaction temperature is usually 250-500°C, preferably 300-450°C, more preferably 300-400°C. When the temperature is lower than 250°C, reaction rate is not sufficient and selectivity of ⁇ -caprolactam tends to decrease and when it is higher than 500°C, selectivity of ⁇ -caprolactam tends to decrease.
- the present process is carried out under pressure, atmospheric pressure or reduced pressure, but is usually carried out under a pressure of 0.05-10 kg/cm2.
- Isolation of ⁇ -caprolactam from the reaction mixture and purification thereof are carried out, for example, by cooling and condensing the reaction product gas, followed by extraction, distillation or crystallization.
- Ammonia and methylamines added to the reaction system are separated and recovered from the reaction product and reused. For example, ammonia and methylamines are recovered in a gaseous state in cooling and condensing the reaction product gas.
- the catalyst having small activity which is caused by use for long time is easily reactivated to the initial capacity by being calcined in molecular oxygen-containing gas, for example, air stream or a molecular oxygen-containing gas to which alcohols such as methanol are added.
- molecular oxygen-containing gas for example, air stream or a molecular oxygen-containing gas to which alcohols such as methanol are added.
- the reactivated catalyst is repeatedly used.
- ⁇ -caprolactam is obtained with high selectivity and life of the catalysts is greatly prolonged even under such conditions that cyclohexanon oxime reacts with high conversion.
- a white solid product was filtered off and washed continuously with distilled water until pH of filtrate reached about 7.
- the white solid was dried and calcined in an air stream at 500-530°C for 4 hours to obtain powdery white crystals (27 g) which were identified to be pentasil type zeolite by powder X-ray diffraction.
- Al content was 3 ppm according to atomic absorption spectroscopy assay.
- reaction tube was fed a mixed solution of cyclohexanone oxime/methanol (1/1. 8 in weight ratio) at a rate of 8.4 g/hr under feeding the above mixed gas to carry out a reaction.
- the space velocity WHSV of cyclohexanone oxime was 8 hr ⁇ 1 and temperature of the catalyst bed (reaction temperature) was 350°C.
- feeding of all materials was stopped to terminate the react ion.
- the react ion product was trapped and collected under water cooling and was analyzed by gas chromatography.
- Selectivity of ⁇ -caprolactam (%) [Z/(X-Y)] x 100
- the catalyst bed was heated to 430°C under feeding to the reaction tube a mixed gas of nitrogen, air and methanol (methanol concentration 3.8 vol%: saturated concentration at 0°C) obtained by bubbling a mixed gas of nitrogen gas (2.5 l/hr) and air (2.5 l/hr) in methanol kept at 0°C.
- the catalyst bed was treated at that temperature for 23 hours, thereby to remove carbonaceous materials formed on the catalyst.
- reaction tube were separately but simultaneously fed a mixed solution of cyclohexanone oxime/methanol (1/1.2 in weight ratio) at a rate of 6.6 g/hr and methanol at a rate of 1.8 g/hr under feeding the above mixed gas to carry out a reaction.
- the space velocity WHSV of cyclohexanone oxime was 8 hr ⁇ 1 and temperature of the catalyst bed ( reaction temperature) was 350°C.
- feeding of all materials was stopped to terminate the reaction.
- the reaction product was trapped and collected using water cooling and was analyzed by gas chromatography.
- Carbonaceous materials formed on the catalyst were removed in the same manner as in Example 1 except that the treating time was 96 hours in place of 23 hours.
- reaction temperature 350°C.
- feeding of all materials was stopped to terminate the reaction.
- the reaction product was trapped and collected using water cooling and was analyzed by gas chromatography.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Other In-Based Heterocyclic Compounds (AREA)
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP312493/91 | 1991-11-27 | ||
| JP31249391 | 1991-11-27 | ||
| JP31249291 | 1991-11-27 | ||
| JP31249291 | 1991-11-27 | ||
| JP312492/91 | 1991-11-27 | ||
| JP31249391A JP3221021B2 (ja) | 1991-11-27 | 1991-11-27 | ε−カプロラクタムの製造方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0544531A1 true EP0544531A1 (de) | 1993-06-02 |
| EP0544531B1 EP0544531B1 (de) | 2000-04-05 |
Family
ID=26567192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92310819A Expired - Lifetime EP0544531B1 (de) | 1991-11-27 | 1992-11-26 | Verfahren zur Herstellung von Epsilon-Caprolactam durch Beckmann-Umlagerung in der Gasphase in Gegenwart eines Zeolithkatalysators und einer stickstoffhaltigen Verbindung |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5354859A (de) |
| EP (1) | EP0544531B1 (de) |
| DE (1) | DE69230876T2 (de) |
| TW (1) | TW213896B (de) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1028108A1 (de) * | 1999-02-09 | 2000-08-16 | Sumitomo Chemical Company, Limited | Verfahren zur Herstellung von epsilon-Caprolactam |
| EP1142871A1 (de) * | 1998-12-25 | 2001-10-10 | Mitsubishi Chemical Corporation | Oxid-katalysatoren und ein verfahren zur herstellung von epsilon-caprolactam mit ihnen |
| WO2002064560A1 (en) * | 2001-02-14 | 2002-08-22 | Asahi Kasei Kabushiki Kaisha | PROCESS FOR PREPARATION OF ε-CAPROLACTAM |
| EP1352902A1 (de) * | 2002-02-27 | 2003-10-15 | Sumitomo Chemical Company, Limited | Verfahren zur Herstellung von Epsilon-Caprolactam und Katalysator für diese Herstellung |
| EP1582515A1 (de) * | 2004-03-30 | 2005-10-05 | Sumitomo Chemical Company, Limited | Verfahren zur Herstellung von epsilon-Caprolactam |
| EP1593433A1 (de) | 2004-02-16 | 2005-11-09 | Sumitomo Chemical Company, Limited | Verfahren zur Herstellung von Epsilon-caprolactam und Verfahren zur Reaktivierung eines Katalysators zur Herstellung von Epsilon-caprolactam |
| EP1875964A1 (de) | 2006-07-04 | 2008-01-09 | Sumitomo Chemical Company, Limited | Verfahren zur Wiederherstellung eines Katalysators zur Herstellung von A-Caprolactam und Verfahren zur Herstellung von E-Caprolactam |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7022844B2 (en) | 2002-09-21 | 2006-04-04 | Honeywell International Inc. | Amide-based compounds, production, recovery, purification and uses thereof |
| KR100503512B1 (ko) * | 2002-11-15 | 2005-07-25 | 주식회사 카프로 | 금속 이온이 담지된 세공성 촉매, 이의 제조방법 및 이를이용한 ε-카프로락탐의 제조방법 |
| DE102008060340A1 (de) | 2008-12-03 | 2010-06-10 | Wolfgang F. Prof. Dr. Hölderich | Herstellung von Lactamen und Carbonsäureamide durch Beckmann-Umlagerung von Oximen in Gegenwart von Nb-Katalysatoren |
| US9073867B2 (en) | 2011-04-09 | 2015-07-07 | Amyris, Inc. | Process for preparing caprolactam and polyamides therefrom |
| CN103889950A (zh) * | 2011-10-17 | 2014-06-25 | 住友化学株式会社 | ε-己内酰胺的制造方法 |
| DE102015005238A1 (de) | 2015-04-24 | 2016-10-27 | Wolfgang Hölderich | Herstellung von Lactamen durch Beckmann-Umlagerung von Oximen |
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| EP0234088A2 (de) * | 1985-08-28 | 1987-09-02 | Sumitomo Chemical Company, Limited | Produktion von E-Caprolactam |
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| EP0242960A2 (de) * | 1986-04-21 | 1987-10-28 | Sumitomo Chemical Company, Limited | Produktion von Epsilon-Kaprolaktam |
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| JPH02250866A (ja) | 1989-03-23 | 1990-10-08 | Sumitomo Chem Co Ltd | ε―カプロラクタムの製造法 |
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| EP0494535A1 (de) | 1990-12-26 | 1992-07-15 | Sumitomo Chemical Company, Limited | Verfahren zur Herstellung von Epsilon-caprolactam und Aktivierung von festen Katalysatoren dafür |
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| US2234566A (en) * | 1938-07-23 | 1941-03-11 | Du Pont | Catalytic process for the production of caprolactam, amino-capronitrile and hexamethylene diamine |
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- 1992-11-13 TW TW081109063A patent/TW213896B/zh not_active IP Right Cessation
- 1992-11-25 US US07/981,476 patent/US5354859A/en not_active Expired - Lifetime
- 1992-11-26 DE DE69230876T patent/DE69230876T2/de not_active Expired - Lifetime
- 1992-11-26 EP EP92310819A patent/EP0544531B1/de not_active Expired - Lifetime
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| EP0234088A2 (de) * | 1985-08-28 | 1987-09-02 | Sumitomo Chemical Company, Limited | Produktion von E-Caprolactam |
| EP0236092A2 (de) * | 1986-02-27 | 1987-09-09 | Sumitomo Chemical Company, Limited | Verfahren zur Herstellung von E-Kaprolaktam |
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| EP0369364A2 (de) * | 1988-11-15 | 1990-05-23 | Süd-Chemie Ag | Katalysator auf der Basis von kristallinem Alumosilikat |
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| JPH02275850A (ja) | 1989-01-26 | 1990-11-09 | Sumitomo Chem Co Ltd | ε―カプロラクタムの製法 |
| EP0388070A1 (de) * | 1989-03-08 | 1990-09-19 | Sumitomo Chemical Company, Limited | Verfahren zur Regenerierung von Katalysatoren |
| JPH02250866A (ja) | 1989-03-23 | 1990-10-08 | Sumitomo Chem Co Ltd | ε―カプロラクタムの製造法 |
| EP0494535A1 (de) | 1990-12-26 | 1992-07-15 | Sumitomo Chemical Company, Limited | Verfahren zur Herstellung von Epsilon-caprolactam und Aktivierung von festen Katalysatoren dafür |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1142871A1 (de) * | 1998-12-25 | 2001-10-10 | Mitsubishi Chemical Corporation | Oxid-katalysatoren und ein verfahren zur herstellung von epsilon-caprolactam mit ihnen |
| EP1142871A4 (de) * | 1998-12-25 | 2002-04-24 | Mitsubishi Chem Corp | Oxid-katalysatoren und ein verfahren zur herstellung von epsilon-caprolactam mit ihnen |
| EP1028108A1 (de) * | 1999-02-09 | 2000-08-16 | Sumitomo Chemical Company, Limited | Verfahren zur Herstellung von epsilon-Caprolactam |
| US6265574B1 (en) | 1999-02-09 | 2001-07-24 | Sumitomo Chemical Company, Limited | Process for producing ε-caprolactam |
| CN100379726C (zh) * | 1999-02-09 | 2008-04-09 | 住友化学工业株式会社 | ε-己内酰胺的生产方法 |
| US6894163B2 (en) | 2001-02-14 | 2005-05-17 | Asahi Kasei Kabushiki Kaisha | Process for preparation of epsilon-caprolactam |
| WO2002064560A1 (en) * | 2001-02-14 | 2002-08-22 | Asahi Kasei Kabushiki Kaisha | PROCESS FOR PREPARATION OF ε-CAPROLACTAM |
| EP1352902A1 (de) * | 2002-02-27 | 2003-10-15 | Sumitomo Chemical Company, Limited | Verfahren zur Herstellung von Epsilon-Caprolactam und Katalysator für diese Herstellung |
| US6946553B2 (en) | 2002-02-27 | 2005-09-20 | Sumitomo Chemical Company, Limited | Process for producing ε-caprolactam and catalyst for the production |
| EP1593433A1 (de) | 2004-02-16 | 2005-11-09 | Sumitomo Chemical Company, Limited | Verfahren zur Herstellung von Epsilon-caprolactam und Verfahren zur Reaktivierung eines Katalysators zur Herstellung von Epsilon-caprolactam |
| US7026474B2 (en) | 2004-02-16 | 2006-04-11 | Sumitomo Chemical Company, Limited | Method for producing ε-caprolactam and method for reactivating catalyst for production of ε-caprolactam |
| EP1582515A1 (de) * | 2004-03-30 | 2005-10-05 | Sumitomo Chemical Company, Limited | Verfahren zur Herstellung von epsilon-Caprolactam |
| US7189845B2 (en) | 2004-03-30 | 2007-03-13 | Sumitomo Chemical Company, Limited | Method for producing ε-caprolactam |
| EP1875964A1 (de) | 2006-07-04 | 2008-01-09 | Sumitomo Chemical Company, Limited | Verfahren zur Wiederherstellung eines Katalysators zur Herstellung von A-Caprolactam und Verfahren zur Herstellung von E-Caprolactam |
Also Published As
| Publication number | Publication date |
|---|---|
| TW213896B (de) | 1993-10-01 |
| DE69230876D1 (de) | 2000-05-11 |
| DE69230876T2 (de) | 2000-08-03 |
| EP0544531B1 (de) | 2000-04-05 |
| US5354859A (en) | 1994-10-11 |
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